US20130344354A1 - Hybrid Anodes for Energy Storage Devices - Google Patents
Hybrid Anodes for Energy Storage Devices Download PDFInfo
- Publication number
- US20130344354A1 US20130344354A1 US13/532,206 US201213532206A US2013344354A1 US 20130344354 A1 US20130344354 A1 US 20130344354A1 US 201213532206 A US201213532206 A US 201213532206A US 2013344354 A1 US2013344354 A1 US 2013344354A1
- Authority
- US
- United States
- Prior art keywords
- carbon
- energy storage
- storage device
- electrode
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004146 energy storage Methods 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 152
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 229910052742 iron Inorganic materials 0.000 claims description 57
- 229910002804 graphite Inorganic materials 0.000 claims description 48
- 239000010439 graphite Substances 0.000 claims description 48
- 229910052804 chromium Inorganic materials 0.000 claims description 42
- 229910052748 manganese Inorganic materials 0.000 claims description 42
- 229910052744 lithium Inorganic materials 0.000 claims description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- 229910052749 magnesium Inorganic materials 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 150000003464 sulfur compounds Chemical class 0.000 claims description 17
- 229910013458 LiC6 Inorganic materials 0.000 claims description 16
- 238000009830 intercalation Methods 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 16
- 230000002687 intercalation Effects 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- -1 or Co) Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910021385 hard carbon Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 229910011823 Li2-x(Fe1-yMny)P2O7 Inorganic materials 0.000 claims description 6
- 229910010359 Li2MSO4 Inorganic materials 0.000 claims description 6
- 229910010364 Li2MSiO4 Inorganic materials 0.000 claims description 6
- 229910011303 Li3V2-xMx(PO4)3 Inorganic materials 0.000 claims description 6
- 229910011675 Li4-xMxTi5O12 Inorganic materials 0.000 claims description 6
- 229910013351 LiMSO4F Inorganic materials 0.000 claims description 6
- 229910014192 LiMn2-y Inorganic materials 0.000 claims description 6
- 229910012970 LiV3O8 Inorganic materials 0.000 claims description 6
- 229910001319 LiVPO4F Inorganic materials 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 44
- 230000001351 cycling effect Effects 0.000 description 21
- 229910003003 Li-S Inorganic materials 0.000 description 19
- 239000011888 foil Substances 0.000 description 14
- 229920001021 polysulfide Polymers 0.000 description 12
- 239000005077 polysulfide Substances 0.000 description 12
- 150000008117 polysulfides Polymers 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 210000004754 hybrid cell Anatomy 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001216 Li2S Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 206010014415 Electrolyte depletion Diseases 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- lithium ion batteries exhibit insufficient capacities to enable the extended driving range demanded by the electric vehicle market.
- Various types of energy storage devices show promise, including those having electrodes comprising Li, Na, Zn, Si, Mg, Al, Sn, and Fe.
- lithium sulfur batteries are attractive because of the large specific capacity and energy density.
- some obstacles must be overcome before any of these devices can successfully be implemented.
- the formation of soluble long chain polysulfides during charge/discharge can lead to the gradual loss of active mass from the cathode into the electrolyte and onto the lithium anode, continuously forming a passivation film.
- the energy storage devices each comprise a cathode separated from the hybrid anode by a separator.
- the hybrid anode comprises a carbon electrode connected to a metal electrode, thereby resulting in an equipotential between the carbon and metal electrodes.
- equipotential can encompass minor deviations from a theoretical equipotential (i.e., a pseudo-equipotential).
- the carbon electrode and metal electrode should, in principle, have the same potential. However, in some instances, it can take significant time to reach equilibrium and equal potentials. Thus, the potentials of the carbon and metal electrodes may be very close, but may not be quite equal.
- the carbon and metal electrodes are connected in parallel to function as an anode.
- the carbon and metal electrodes can be separated by a separator or can be exposed directly one to another.
- the carbon and metal electrodes can be in direct contact or can be separated by some amount of space.
- the carbon and metal electrodes remain in contact during operation and not merely prior to initial cycling.
- the metal electrode is not merely an initial source of metal to be incorporated into the carbon electrode (i.e., intercalated, deposited, etc.).
- the carbon electrode functions as a drain for metal ions and helps to decouple the contamination problem, or undesired reactions, on the metal anode throughout operation of the device.
- the carbon electrode can comprise graphite, hard carbon, carbon black, carbon fibers, graphene, and other conductive carbonaceous materials.
- the metal electrode can comprise Li, Na, Zn, Si, Mg, Al, Sn, and Fe.
- the metal electrode comprises Li.
- the carbon electrode further comprises metalated carbon.
- the carbon electrode can comprise lithiated carbon.
- the carbon electrode can further comprise metal ions intercalated therein, deposited thereon, or both.
- the metal ions comprise lithium ions.
- the carbon electrode is maintained in a metalated carbon state.
- Traditional energy storage devices are typically metalated during a charge process and demetalated during a discharge process.
- loss of metalated carbon from the carbon electrode is compensated by the metal electrode of the hybrid anode.
- the carbon electrode can be viewed as a sink to drain metal ions from the metal electrode.
- metal ions can return to the metal anode instead of to the carbon electrode as metalated carbon when charging.
- the cathode comprises sulfur and/or sulfur compounds.
- the sulfur compound can comprise polysulfides.
- polysulfides can comprise Li x S y , wherein x is from 0 to 4, and y is from 1 to 8.
- Devices having cathodes comprising sulfur and/or sulfur compounds, according to embodiments described herein, can be configured to exhibit a reversible capacity greater than, or equal to, 800 mAh g ⁇ 1 at 0.8 C during operation. Other embodiments can exhibit a capacity greater than, or equal to, 750 mAh g ⁇ 1 for more than 200 cycles.
- the cathode can comprise a lithium intercalation material, or a material capable of lithium intercalation.
- a lithium intercalation material or a material capable of lithium intercalation.
- One embodiment of the present invention includes a lithium-sulfur energy storage device having a cathode comprising sulfur, sulfur compounds, or both, that is separated from a hybrid anode by a separator.
- the hybrid anode comprises a carbon electrode connected to a lithium metal electrode, thereby resulting in an equipotential between the carbon and lithium metal electrodes.
- the hybrid anode is further configured to comprise lithiated carbon at the carbon electrode during operation of the energy storage device.
- lithiated carbon includes, but is not limited to, LiC 6 .
- the sulfur compound can comprise Li x S y , wherein x is from 0 to 4, and y is from 1 to 8.
- the carbon electrode comprises graphite.
- Another embodiment includes a lithium-ion energy storage device having a cathode comprising a lithium intercalation material that is separated from a hybrid anode by a separator.
- the hybrid anode comprises a carbon electrode connected to a lithium metal electrode, thereby resulting in an equipotential between the carbon and lithium metal electrodes.
- the hybrid anode further comprises lithiated carbon at the carbon electrode. Examples of materials for the carbon electrode can include, but are not limited to, graphite, hard carbon, carbon black, carbon fibers, graphene, and combinations thereof.
- the lithiated carbon can, for example, comprise LiC 6 .
- This document also describes methods of operating an energy storage device having a cathode separated by a separator from a hybrid anode.
- the methods are characterized by electrically connecting a carbon electrode and a metal electrode, thereby resulting in an equipotential between the carbon and metal electrodes.
- the methods can further comprise metalating the carbon electrode with metal from the metal electrode, thereby forming metalated carbon.
- the carbon electrode is maintained in a metalated state throughout operation of the energy storage device.
- the method can comprise extracting metal ions from the metal electrode through the metalated carbon of the carbon electrode.
- the method can comprise intercalating metal ions in the carbon electrode, depositing metal ions on the carbon electrode, or both.
- the cathode comprises sulfur and/or sulfur compounds and the metal electrode comprises lithium.
- the metalated carbon can comprise LiC 6 and/or the sulfur compound can comprise Li x S y , wherein x is from 0 to 4, and y is from 1 to 8.
- the cathode can comprise a lithium intercalation compound.
- FIGS. 1A-1D are discharge-charge profiles, cycle stability and Coulombic efficiency plots for traditional Li—S cells at various current rates.
- FIGS. 2A-2C include SEM micrographs of lithium foil anodes after cycling in traditional Li—S cells.
- FIGS. 3A and 3B depict different configurations of hybrid anodes in energy storage devices according to embodiments of the present invention.
- FIGS. 4A-4D are discharge-charge profiles, cycle stability and Coulombic efficiency plots at various current rates for Li—S battery having hybrid anodes according to embodiments of the present invention.
- FIG. 5 is a plot of discharge capacity as a function of cycle number for a Li—S battery having a hybrid anode according to embodiments of the present invention with varying amounts of carbon in the structure.
- FIGS. 6A-6D include SEM micrographs of hybrid anodes before and after operation of Li—S batteries according to embodiments of the present invention.
- FIG. 7 is a plot of discharge capacity as a function of cycle number for Li-ion cells containing standard graphite anodes versus the hybrid anode according to embodiments of the present invention.
- a lithium sulfur battery employs a cathode comprising sulfur and/or sulfur compounds and a hybrid anode comprising a graphite electrode and a lithium metal electrode connected with each other.
- the battery is configured such that the graphite is in the lithiated state during operation and functions as a dynamic “pump” that supplies Li + ions while minimizing direct contact between soluble polysulfides and Li metal. Therefore, the continuous corrosion and contamination of Li anode during repeated cycling can be largely mitigated. As a result, excellent electrochemical performances have been observed.
- the as-designed Li—S cell retains a reversible capacity of greater than 800 mAh g ⁇ 1 corresponding to only 11% fade along with a high Coulombic efficiency of above 99%.
- a similar hybrid anode can be applied in many other energy storage systems that traditionally use metal anodes.
- the continuous loss of active material i.e., sulfur on a Li anode
- active material i.e., sulfur on a Li anode
- FIGS. 1A-1D The electrochemical characteristics of traditional Li—S cells containing sulfur-impregnated mesoporous carbon cathodes are plotted in FIGS. 1A-1D . Morphologies of the Li metal after cycling of these traditional cells are provided in FIG. 2 .
- Typical voltage profiles of sulfur are observed in FIG. 1A (i.e. 2.3 V for transition from S to Li 2 S 4 and 2.0 V for the further reduction to Li 2 S 2 /Li 2 S).
- FIG. 2A shows the top view of the Li anode after cycling.
- the surface is covered with a thick passivation layer and is characterized by large cracks caused by electrolyte depletion.
- FIG. 2B reveals that the Li foil became highly porous, consisting of tubular and irregular particles.
- the cross-sectional SEM micrograph in FIG. 2C shows that the passivation layer is more than 100 ⁇ m thick. More importantly, at higher magnification, cross-sectional SEM and sulfur elemental mapping indicate an extensive (>100 ⁇ m thick) reaction zone where the Li metal is penetrated by sulfur.
- a carbon electrode 301 is directly connected with a metal electrode 302 and used together as a hybrid anode 307 .
- An anode separator 305 can be placed between the carbon and metal electrodes. Alternatively, the separator can be absent (see FIG. 3B ).
- the carbon electrode comprises metal ions 306 transferred from the metal electrode and intercalated and/or adsorbed at the carbon electrode. In some instances, a region around the graphite electrode can develop wherein byproducts can accumulate, deposit and/or contaminate. During discharge, metal ions will move 309 toward the cathode 303 through a separator 304 .
- circular arrows 310 depict the shuttling of dissolved polysulfides between the anode and cathode.
- the carbon electrode 301 and the metal electrode 302 can be in direct contact (with or without an anode separator). Once immersed in electrolyte, the carbon will be immediately discharged and will be maintained in the metalated state because the hybrid anode is in one sense a shorted metal/carbon cell.
- FIG. 4A shows the voltage profiles at different current densities of a Li—S cell utilizing a hybrid anode as described herein.
- the cell includes a cathode comprising sulfur and/or sulfur compounds and a hybrid anode.
- the hybrid anode comprises a graphite electrode and a lithium metal electrode.
- the cell delivered a reversible capacity of greater than 900 mAh g ⁇ 1 at 1.37 A g ⁇ 1 ( ⁇ 0.8 C). Even at a high rate of 13.79 A g ⁇ 1 ( ⁇ 8C), more than 450 mA g ⁇ 1 capacity was demonstrated.
- far more stable discharge/charge profiles of sulfur are observed in these cells (see FIG. 4B ).
- the carbon electrode is metalated.
- the graphite electrode can comprise lithiated carbon.
- the lithiated carbon can be a physical barrier that interferes with the traditional concentration gradient of soluble species in the electrolyte. Physical absorption of polysulfides on the graphite surface reduces further transport of soluble intermediates onto the lithium metal anode. Control cells in which Li foil and graphite electrodes were not connected in parallel, yet were in physical contact, confirm that embodiments of the present invention can minimize the reaction of polysulfides with the Li metal anode. When compared with traditional Li—S cells (as shown in FIG.
- cycling performance is only slightly improved indicating that the graphite forms a partial physical/chemical barrier, even when not connected to the lithium metal anode, that can slow down adverse polysulfide reactions with Li metal, although not to the extent seen in the hybrid anodes described herein.
- a metalated carbon electrode can function as a pump to supply metal ions during discharge.
- the lithiated graphite in Li—S batteries having hybrid anodes according to embodiments of the present invention can supply Li + during discharge.
- Li + should first move from Li metal to the graphite during discharge in the Li—S cells.
- Li + ions will be released from both LiC 6 in the graphite electrode and from Li metal because the surface concentration of Li + ions around either LiC 6 or Li surfaces are both very low (close to zero) at high current densities.
- the 0.02 V voltage difference may be negligible and Li + ions may be largely provided by the lithiated graphite considering their preferred position in the cell configuration. Because the carbon electrode is shorted with the metal electrode, once Li + is depleted from the graphite, it can be quickly replenished from the Li metal. In other words, lithiated graphite can function as a dynamic “pump” that continuously drains Li + ions from Li metal reservoir and ejects Li + ions on demand.
- the carbon materials have an electrochemical reduction potential very close to Li/Li + (to facilitate Li + extraction) combined with a low surface area to reduce undesired side reactions with sulfur species.
- Li + ions diffuse back to the metal electrode where they are redeposited.
- One issue is to determine if the Li ions will preferentially deposit on the Li-foil or the lithiated graphite portions of the hybrid anode.
- SEM micrographs in FIG. 6 show the “as prepared” graphite surface of the hybrid anode ( FIG. 6A ) and the same surface after 1000 charge/discharge cycles at a 1C rate ( FIG. 6B ) in a Li—S cell. Little morphological change has occurred after extensive cycling yet the surface is rich in sulfur as determined by elemental mapping. After long-term cycling, the morphology of the corresponding Li-foil surface (facing the graphite) is shown in FIGS.
- the hybrid anodes described herein can be also utilized in lithium-ion batteries having cathodes comprising lithium intercalation compounds.
- a series of test cells using commercially-available materials were prepared.
- the cathodes in all cells were prepared using a pyrolytic carbon-coated, nanosized, LiFePO 4 powder (LFP).
- LFP cathodes were then paired with one of three test anodes; (1) Li foil, (2) graphite, or (3) Li foil+graphite configured as a hybrid anode according to embodiments described herein.
- the cathodes were prepared by coating well-dispersed slurries containing 80 wt % LFP powder, 10 wt % Super-P® conductive carbon black, and 10 wt % polyvinylidene difluoride (PVDF) binder dissolved in N-methyl-2-pyrrolidinone (NMP) onto a thin aluminum-foil current collector.
- LFP cathode was dried at 70° C. under vacuum for 12 h.
- a hydraulic press was used to compact the LFP-Al electrode to minimize electrode contact resistance.
- the hybrid Li-carbon anodes carbon was pasted or coated onto a thin porous metallic mesh (current collector) and then electrically connected to a Li metal foil with a commercial separator sandwiched between the graphite and Li foil.
- the carbon material was high power CPreme® graphite material G5 from ConocoPhillips coating/graphitization technology.
- the separator was not necessary and the hybrid anode could be constructed by simply laminating Li foil to the graphite. Good bonding between the metallic mesh, graphite and conductive carbon minimizes de-lamination, pinholes, and diminished internal cell resistance.
- the porous metal-carbon mesh electrode was prepared by coating well-dispersed slurries containing 80 wt % CPreme® G5 graphite powder, 10 wt % Super-P® conducting carbon black, and 10 wt % PVDF dissolved in NMP onto thin porous copper mesh.
- the carbon electrodes were dried at 70° C. under vacuum for 12 h, and then hot pressed to form the final carbon laminated electrode.
- the porous carbon-metallic mesh electrode can be prepared by hot pressing of free-standing carbon thin films onto the thin cooper mesh.
- the carbon-PTFE composite powder was first obtained by drying well-dispersed slurries containing 80 wt % CPreme® G5 graphite powder, 10 wt % Super-P Li conducting carbon black, and 10 wt % PTFE emulsion diluted in distilled water. The powder was then rolled to form carbon-PTFE free-standing thin films with the desired thickness by a Cavallin flat roller. Finally, the film was hot pressed onto the thin metallic mesh using a Carver hot press.
- Lithium metal disks ( ⁇ 15 size and 0.5 mm thickness) were used as the anode for traditional Li-LFP cells and as the metal electrode of the hybrid anode for hybrid cells.
- a microporous membrane (Celgard 3501®, 25 ⁇ m thickness) was used as the separator.
- the LFP cathode, a first separator, carbon-metallic mesh electrode, thin metallic ring, a second separator, and lithium foil were punched into ⁇ 15, ⁇ 19, ⁇ 15, ⁇ 15, ⁇ 13 and ⁇ 15 sizes, respectively, and electrolyte was added into each cell layer-by-layer, using a pipette.
- the metallic mesh was calendared and punched into metallic rings ⁇ 25 ⁇ m in thickness to form the electrical contact between the two components of the hybrid anode.
- the metallic ring can be replaced by small pieces of metallic mesh to make edge point contact between the lithium foil and carbon-metallic mesh electrode.
- the layers of the hybrid anode can be separated by the second separator, or sandwiched together directly. All cell components were then carefully aligned, integrated and sealed using a compact hydraulic crimping machine to form the final test device.
- Electrochemical tests were performed using 2325 coin cells in an ambient environment.
- the galvanostatic discharge-charge test was conducted using a BT-2043 Arbin® Battery Testing System.
- the hybrid cells and half cells were cycled at different current rates in the voltage interval of 2.5-4.2V. Due to the initial irreversible loss observed for the control cells, the G5-LFP control cells with graphite anodes were tested between 2-4.2V. All capacity values were calculated on the basis of LFP mass. After cycling, several of the coin cells were disassembled in the charged or discharged state for further analysis.
- FIG. 7 shows the long-term cycling performance of the three tests cells at high charge/discharge rate (i.e., 38C).
- the hybrid anode described herein results in greatly improved capacity retention, showing little fade after 3500 cycles.
- the specific capacity of cells containing graphite, or Li-foil, anodes faded to near zero within 500 cycles. This shows that the hybrid anode design is useful in extending the performance and cycle life of cells/batteries using Li-ion chemistries.
Abstract
Description
- This invention was made with Government support under Contract DE-AC0576RLO1830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
- Practical implementation of a number of important technologies has been slowed by limitations in state-of-the-art energy storage devices. For example, current lithium ion batteries exhibit insufficient capacities to enable the extended driving range demanded by the electric vehicle market. Various types of energy storage devices show promise, including those having electrodes comprising Li, Na, Zn, Si, Mg, Al, Sn, and Fe. In another example, lithium sulfur batteries are attractive because of the large specific capacity and energy density. However, some obstacles must be overcome before any of these devices can successfully be implemented. In lithium sulfur batteries, the formation of soluble long chain polysulfides during charge/discharge can lead to the gradual loss of active mass from the cathode into the electrolyte and onto the lithium anode, continuously forming a passivation film. As a result, severe self-discharge and capacity decay upon cycling are usually observed, hindering the practical application of lithium sulfur batteries. Similarly, in lithium-ion batteries, metal plating on the anode, particularly at high charge rates, can lead to cell shorting and combustion—thus presenting a major safety concern. Improved energy storage devices with stable electrochemical performance and improved safety are needed to enable the devices requiring electrical power.
- This document describes methods of operating energy storage devices as well as energy storage devices having hybrid anodes that address at least the problems of active material consumption and anode passivation. The energy storage devices each comprise a cathode separated from the hybrid anode by a separator. The hybrid anode comprises a carbon electrode connected to a metal electrode, thereby resulting in an equipotential between the carbon and metal electrodes. As used herein, equipotential can encompass minor deviations from a theoretical equipotential (i.e., a pseudo-equipotential). For example, the carbon electrode and metal electrode should, in principle, have the same potential. However, in some instances, it can take significant time to reach equilibrium and equal potentials. Thus, the potentials of the carbon and metal electrodes may be very close, but may not be quite equal.
- In one sense, the carbon and metal electrodes are connected in parallel to function as an anode. The carbon and metal electrodes can be separated by a separator or can be exposed directly one to another. Furthermore, the carbon and metal electrodes can be in direct contact or can be separated by some amount of space. In particular embodiments, the carbon and metal electrodes remain in contact during operation and not merely prior to initial cycling. For example, the metal electrode is not merely an initial source of metal to be incorporated into the carbon electrode (i.e., intercalated, deposited, etc.). According to one embodiment, the carbon electrode functions as a drain for metal ions and helps to decouple the contamination problem, or undesired reactions, on the metal anode throughout operation of the device.
- The carbon electrode can comprise graphite, hard carbon, carbon black, carbon fibers, graphene, and other conductive carbonaceous materials. The metal electrode can comprise Li, Na, Zn, Si, Mg, Al, Sn, and Fe. Preferably, the metal electrode comprises Li.
- In some embodiments, the carbon electrode further comprises metalated carbon. For example, the carbon electrode can comprise lithiated carbon. Alternatively, or in addition, the carbon electrode can further comprise metal ions intercalated therein, deposited thereon, or both. In one embodiment, the metal ions comprise lithium ions.
- Preferably, the carbon electrode is maintained in a metalated carbon state. Traditional energy storage devices are typically metalated during a charge process and demetalated during a discharge process. However, according to the present embodiment, loss of metalated carbon from the carbon electrode is compensated by the metal electrode of the hybrid anode. Accordingly, the carbon electrode can be viewed as a sink to drain metal ions from the metal electrode. Furthermore, in some instances, metal ions can return to the metal anode instead of to the carbon electrode as metalated carbon when charging.
- In one embodiment, the cathode comprises sulfur and/or sulfur compounds. For instance, the sulfur compound can comprise polysulfides. In one example, polysulfides can comprise LixSy, wherein x is from 0 to 4, and y is from 1 to 8. Devices having cathodes comprising sulfur and/or sulfur compounds, according to embodiments described herein, can be configured to exhibit a reversible capacity greater than, or equal to, 800 mAh g−1 at 0.8 C during operation. Other embodiments can exhibit a capacity greater than, or equal to, 750 mAh g−1 for more than 200 cycles.
- In another embodiment, the cathode can comprise a lithium intercalation material, or a material capable of lithium intercalation. Examples can include, but are not limited to, Li4-xMxTi5O12 (M=Mg, Al, Ba, Sr, or Ta; 0≦x≦1), MnO2, V2O5, V6O13, LiV3O8, LiMC1 xMC2 1-xPO4 (MC1 or MC2=Fe, Mn, Ni, Co, Cr, or Ti; 0≦x≦1), Li3V2-xMx(PO4)3 (M=Cr, Co, Fe, Mg, Y, Ti, Nb, or Ce; 0≦x≦1), LiVPO4F, LiMC1 xMC2 1-xO2 ((MC1 or MC2=Fe, Mn, Ni, Co, Cr, Ti, Mg, Al; 0≦x≦1), LiMC1 xMC2 yMC3 1-x-yO2 ((MC1, MC2, MC3=Fe, Mn, Ni, Co, Cr, Ti, Mg, or Al; 0≦x≦1; 0≦y≦1), LiMn2-yXyO4 (X═Cr, Al, or Fe, 0≦y≦1), LiNi0.5-yXyMn1.5O4 (X═Fe, Cr, Zn, Al, Mg, Ga, V, or Cu; 0≦y<0.5), xLi2MnO3.(1-x)LiMC1 yMC2 zMC3 1-y-zO2 (MC1, MC2, or MC3=Mn, Ni, Co, Cr, Fe, or mixture of; x=0.3-0.5; y≦0.5; z≦0.5), Li2MSiO4 (M=Mn, Fe, or Co), Li2MSO4 (M=Mn, Fe, or Co), LiMSO4F (Fe, Mn, or Co), Li2-x(Fe1-yMny)P2O7 (0≦y≦1), Cr3O8, Cr2O5 and combinations thereof.
- One embodiment of the present invention includes a lithium-sulfur energy storage device having a cathode comprising sulfur, sulfur compounds, or both, that is separated from a hybrid anode by a separator. The hybrid anode comprises a carbon electrode connected to a lithium metal electrode, thereby resulting in an equipotential between the carbon and lithium metal electrodes. The hybrid anode is further configured to comprise lithiated carbon at the carbon electrode during operation of the energy storage device. One example of lithiated carbon, includes, but is not limited to, LiC6. The sulfur compound can comprise LixSy, wherein x is from 0 to 4, and y is from 1 to 8. Preferably, the carbon electrode comprises graphite.
- Another embodiment includes a lithium-ion energy storage device having a cathode comprising a lithium intercalation material that is separated from a hybrid anode by a separator. The hybrid anode comprises a carbon electrode connected to a lithium metal electrode, thereby resulting in an equipotential between the carbon and lithium metal electrodes. Furthermore, the hybrid anode further comprises lithiated carbon at the carbon electrode. Examples of materials for the carbon electrode can include, but are not limited to, graphite, hard carbon, carbon black, carbon fibers, graphene, and combinations thereof. The lithiated carbon can, for example, comprise LiC6. Examples of a lithium intercalation material can include, but are not limited to, Li4-xMxTi5O12 (M=Mg, Al, Ba, Sr, or Ta; 0≦x≦1), MnO2, V2O5, V6O13, LiV3O8, LiMC1 xMC2 1-xPO4 (MC1 or MC2=Fe, Mn, Ni, Co, Cr, or Ti; 0≦x≦1), Li3V2-xMx(PO4)3 (M=Cr, Co, Fe, Mg, Y, Ti, Nb, or Ce; 0≦x≦1), LiVPO4F, LiMC1 xMC2 1-xO2 ((MC1 or MC2=Fe, Mn, Ni, Co, Cr, Ti, Mg, Al; 0≦x≦1), LiMC1 xMC2 yMC3 1-x-yO2 ((MC1, MC2, MC3=Fe, Mn, Ni, Co, Cr, Ti, Mg, or Al; 0≦x≦1; 0≦y≦1), LiMn2-yXyO4 (X═Cr, Al, or Fe, 0≦y≦1), LiNi0.5-yXyMn1.5O4 (X═Fe, Cr, Zn, Al, Mg, Ga, V, or Cu; 0≦y<0.5), xLi2MnO3.(1-x)LiMC1 yMC2 zMC3 1-y-zO2 (MC1, MC2, or MC3=Mn, Ni, Co, Cr, Fe, or mixture of; x=0.3-0.5; y≦0.5; z≦0.5), Li2MSiO4 (M=Mn, Fe, or Co), Li2MSO4 (M=Mn, Fe, or Co), LiMSO4F (Fe, Mn, or Co), Li2-x(Fe1-yMny)P2O7 (0≦y≦1), Cr3O8, Cr2O5, and combinations thereof.
- This document also describes methods of operating an energy storage device having a cathode separated by a separator from a hybrid anode. The methods are characterized by electrically connecting a carbon electrode and a metal electrode, thereby resulting in an equipotential between the carbon and metal electrodes.
- The methods can further comprise metalating the carbon electrode with metal from the metal electrode, thereby forming metalated carbon. Preferably, the carbon electrode is maintained in a metalated state throughout operation of the energy storage device. Further still, the method can comprise extracting metal ions from the metal electrode through the metalated carbon of the carbon electrode. Alternatively, or in addition, the method can comprise intercalating metal ions in the carbon electrode, depositing metal ions on the carbon electrode, or both.
- In a particular embodiment, the cathode comprises sulfur and/or sulfur compounds and the metal electrode comprises lithium. In such embodiments, the metalated carbon can comprise LiC6 and/or the sulfur compound can comprise LixSy, wherein x is from 0 to 4, and y is from 1 to 8. Alternatively, the cathode can comprise a lithium intercalation compound. Examples of lithium intercalation compounds can include, but are not limited to, Li4-xMxTi5O12 (M=Mg, Al, Ba, Sr, or Ta; 0≦x≦1), MnO2, V2O5, V6O13, LiV3O8, LiMC1 xMC2 1-xPO4 (MC1 or MC2=Fe, Mn, Ni, Co, Cr, or Ti; 0≦x≦1), Li3V2-xMx(PO4)3 (M=Cr, Co, Fe, Mg, Y, Ti, Nb, or Ce; 0≦x≦1), LiVPO4F, LiMC1 xMC2 1-xO2 ((MC1 or MC2=Fe, Mn, Ni, Co, Cr, Ti, Mg, Al; 0≦x≦1), LiMC1 xMC2 yMC3 1-x-yO2 ((MC1, MC2, or MC3=Fe, Mn, Ni, Co, Cr, Ti, Mg, or Al; 0≦x≦1; 0≦y≦1), LiMn2-yXyO4 (X═Cr, Al, or Fe, 0≦y≦1), LiNi0.5-yXyMn1.5O4 (X═Fe, Cr, Zn, Al, Mg, Ga, V, or Cu; 0≦y≦0.5), xLi2MnO3.(1-x)LiMC1 yMC2 zMC3 1-y-zO2 (MC1, MC2, or MC3=Mn, Ni, Co, Cr, Fe, or mixture of; x=0.3-0.5; y≦0.5; z≦0.5), Li2MSiO4 (M=Mn, Fe, or Co), Li2MSO4 (M=Mn, Fe, or Co), LiMSO4F (Fe, Mn, or Co), Li2-x(Fe1-yMny)P2O7 (0≦y≦1), Cr3O8, Cr2O5, and combinations thereof.
- The purpose of the foregoing summary is to enable the United States Patent and Trademark Office and the public generally, especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The summary is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
- Various advantages and novel features of the present invention are described herein and will become further readily apparent to those skilled in this art from the following detailed description. In the preceding and following descriptions, the various embodiments, including the preferred embodiments, have been shown and described. Included herein is a description of the best mode contemplated for carrying out the invention. As will be realized, the invention is capable of modification in various respects without departing from the invention. Accordingly, the drawings and description of the preferred embodiments set forth hereafter are to be regarded as illustrative in nature, and not as restrictive.
- Embodiments of the invention are described below with reference to the following accompanying drawings.
-
FIGS. 1A-1D are discharge-charge profiles, cycle stability and Coulombic efficiency plots for traditional Li—S cells at various current rates. -
FIGS. 2A-2C include SEM micrographs of lithium foil anodes after cycling in traditional Li—S cells. -
FIGS. 3A and 3B depict different configurations of hybrid anodes in energy storage devices according to embodiments of the present invention. -
FIGS. 4A-4D are discharge-charge profiles, cycle stability and Coulombic efficiency plots at various current rates for Li—S battery having hybrid anodes according to embodiments of the present invention. -
FIG. 5 is a plot of discharge capacity as a function of cycle number for a Li—S battery having a hybrid anode according to embodiments of the present invention with varying amounts of carbon in the structure. -
FIGS. 6A-6D include SEM micrographs of hybrid anodes before and after operation of Li—S batteries according to embodiments of the present invention. -
FIG. 7 is a plot of discharge capacity as a function of cycle number for Li-ion cells containing standard graphite anodes versus the hybrid anode according to embodiments of the present invention. - The following description includes the preferred best mode of one embodiment of the present invention. It will be clear from this description of the invention that the invention is not limited to these illustrated embodiments but that the invention also includes a variety of modifications and embodiments thereto. Therefore the present description should be seen as illustrative and not limiting. While the invention is susceptible of various modifications and alternative constructions, it should be understood, that there is no intention to limit the invention to the specific form disclosed, but, on the contrary, the invention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the invention as defined in the claims.
- According to one embodiment, a lithium sulfur battery employs a cathode comprising sulfur and/or sulfur compounds and a hybrid anode comprising a graphite electrode and a lithium metal electrode connected with each other. The battery is configured such that the graphite is in the lithiated state during operation and functions as a dynamic “pump” that supplies Li+ ions while minimizing direct contact between soluble polysulfides and Li metal. Therefore, the continuous corrosion and contamination of Li anode during repeated cycling can be largely mitigated. As a result, excellent electrochemical performances have been observed. After 400 cycles, the as-designed Li—S cell retains a reversible capacity of greater than 800 mAh g−1 corresponding to only 11% fade along with a high Coulombic efficiency of above 99%. A similar hybrid anode can be applied in many other energy storage systems that traditionally use metal anodes.
- The continuous loss of active material (i.e., sulfur on a Li anode) was identified as one of the reasons for the poor cycling stability of traditional Li—S systems. The electrochemical characteristics of traditional Li—S cells containing sulfur-impregnated mesoporous carbon cathodes are plotted in
FIGS. 1A-1D . Morphologies of the Li metal after cycling of these traditional cells are provided inFIG. 2 . Typical voltage profiles of sulfur are observed inFIG. 1A (i.e. 2.3 V for transition from S to Li2S4 and 2.0 V for the further reduction to Li2S2/Li2S). When the current density was increased from 0.156 A g−1 to 3.131 A g−1, the discharge capacity decreased from 1200 mAh g−1 to 300 mAh g−1 (seeFIG. 1B ). This cycling performance is expected from traditional mesoporous carbons, which show after about 20 cycles, that capacity retention decreases by approximately 50% and decays very rapidly thereafter when cycled at a low current rate (FIG. 1C ). Capacity fade becomes even worse when the cell is cycled at higher current rates (FIGS. 1B and D). Correspondingly, the Columbic efficiency continues to decline during cycling. - The Li anode, after extensive cycling in this traditional cell, was investigated using SEM as shown in
FIG. 2 .FIG. 2A shows the top view of the Li anode after cycling. The surface is covered with a thick passivation layer and is characterized by large cracks caused by electrolyte depletion. At higher magnification, the micrograph inFIG. 2B reveals that the Li foil became highly porous, consisting of tubular and irregular particles. The cross-sectional SEM micrograph inFIG. 2C shows that the passivation layer is more than 100 μm thick. More importantly, at higher magnification, cross-sectional SEM and sulfur elemental mapping indicate an extensive (>100 μm thick) reaction zone where the Li metal is penetrated by sulfur. Energy dispersive spectroscopy (EDS) and X-ray fluorescence spectroscopy (XPS) suggest that the chemical composition in this surface film is a complicated combination of sulfides, sulfates, fluorides, and carbonates. However, one can conclude that, in addition to the traditional solid electrolyte interface (SEI) film that is usually formed on Li anode surfaces, a large contributor to this passivation layer is from reactions between Li and dissolved polysulfides, which ultimately form a series of complicated sulfur-containing compounds. The continuous formation of porous Li metal during cycling consumes active sulfur in the electrolyte and increases cell impedance. While mesoporous carbon in the cathode can delay the release of soluble polysulfides, the confinement effect from cathode structures are only effective for a limited time. Further cycling leads to sulfur dissolution of the cathode and more importantly, Li+ metal deposition on the porous Li anode, which then increases the resistance of the entire cell. This results in rapid capacity decay (usually observed after 50 cycles) when only cathode modulation is adopted in this system. - Embodiments of the present invention can address, at least in part, these problems. Referring to the embodiment in
FIG. 3A , acarbon electrode 301 is directly connected with ametal electrode 302 and used together as ahybrid anode 307. Ananode separator 305 can be placed between the carbon and metal electrodes. Alternatively, the separator can be absent (seeFIG. 3B ). The carbon electrode comprisesmetal ions 306 transferred from the metal electrode and intercalated and/or adsorbed at the carbon electrode. In some instances, a region around the graphite electrode can develop wherein byproducts can accumulate, deposit and/or contaminate. During discharge, metal ions will move 309 toward thecathode 303 through aseparator 304. In the case of Li—S energy storage devices,circular arrows 310 depict the shuttling of dissolved polysulfides between the anode and cathode. As shown inFIG. 3B , thecarbon electrode 301 and themetal electrode 302 can be in direct contact (with or without an anode separator). Once immersed in electrolyte, the carbon will be immediately discharged and will be maintained in the metalated state because the hybrid anode is in one sense a shorted metal/carbon cell. -
FIG. 4A shows the voltage profiles at different current densities of a Li—S cell utilizing a hybrid anode as described herein. Briefly, the cell includes a cathode comprising sulfur and/or sulfur compounds and a hybrid anode. The hybrid anode comprises a graphite electrode and a lithium metal electrode. The cell delivered a reversible capacity of greater than 900 mAh g−1 at 1.37 A g−1 (˜0.8 C). Even at a high rate of 13.79 A g−1 (˜8C), more than 450 mA g−1 capacity was demonstrated. In addition, far more stable discharge/charge profiles of sulfur are observed in these cells (seeFIG. 4B ).FIGS. 4C and 4D compare the long term cycling performance at different current densities along with Coulombic efficiencies of Li—S cells that contain hybrid anodes according to embodiments of the present invention. A significantly improved cycling stability was observed at all rates. For example, at 0.6125 A g−1, although initial capacity loss is still observed, the capacity becomes extremely stable after 50 cycles, maintaining approximately 850 mAh g−1 for more than 200 cycles (FIG. 4C ). The Columbic efficiency is also nearly 100% over the entire cycling test due to the absence of overcharging in the cells. Similar performance is further observed at higher discharge rates (seeFIG. 4D).which indicates that the shuttle mechanism has been significantly reduced or eliminated. - In some embodiments, the carbon electrode is metalated. For example, in Li—S batteries having a hybrid anode as described herein, the graphite electrode can comprise lithiated carbon. The lithiated carbon can be a physical barrier that interferes with the traditional concentration gradient of soluble species in the electrolyte. Physical absorption of polysulfides on the graphite surface reduces further transport of soluble intermediates onto the lithium metal anode. Control cells in which Li foil and graphite electrodes were not connected in parallel, yet were in physical contact, confirm that embodiments of the present invention can minimize the reaction of polysulfides with the Li metal anode. When compared with traditional Li—S cells (as shown in
FIG. 1C ), cycling performance is only slightly improved indicating that the graphite forms a partial physical/chemical barrier, even when not connected to the lithium metal anode, that can slow down adverse polysulfide reactions with Li metal, although not to the extent seen in the hybrid anodes described herein. - In some embodiments, a metalated carbon electrode can function as a pump to supply metal ions during discharge. For example, the lithiated graphite in Li—S batteries having hybrid anodes according to embodiments of the present invention can supply Li+ during discharge. There is a difference of 0.02 V between the Li+ extraction voltage for LiC6 and Li metal. Thus, theoretically Li+ should first move from Li metal to the graphite during discharge in the Li—S cells. However, at relatively higher rates than those used in conventional lithium batteries, Li+ ions will be released from both LiC6 in the graphite electrode and from Li metal because the surface concentration of Li+ ions around either LiC6 or Li surfaces are both very low (close to zero) at high current densities. Under this condition, the 0.02 V voltage difference may be negligible and Li+ ions may be largely provided by the lithiated graphite considering their preferred position in the cell configuration. Because the carbon electrode is shorted with the metal electrode, once Li+ is depleted from the graphite, it can be quickly replenished from the Li metal. In other words, lithiated graphite can function as a dynamic “pump” that continuously drains Li+ ions from Li metal reservoir and ejects Li+ ions on demand.
- Referring to
FIG. 5 , the electrochemical behavior of a series of hybrid Li—S cells with different graphite loadings were fabricated and compared at a 1C rate. Assuming the stoichiometric reaction S+2Li=Li2S, the molar ratio of S/graphite (C6-) should be ½ because in graphite, 1 mole of Li+ ions has to be accommodated by 6 moles of carbon atoms (LiC6). When S is provided in excess, then the discharge capacity can be determined by LiC6 on the anode side because Li+ ions are mainly provided from LiC6 as described previously. Three different S:C6 ratios (all greater than ½) were compared andFIG. 5 shows that the initial discharge capacity is proportional to the moles of graphite, while the total Li+ ions available from Li metal was identical in all cases. These findings provide further evidence that, during discharge, Li+ ions are provided from lithiated graphite, while Li metal can be considered a Li+ reservoir that refills graphite as Li+ ions are depleted. The major electrochemical reaction occurs between the cathode, which comprises sulfur and/or sulfur compounds, and the carbon electrode, which comprises LiC6, in the hybrid anode. In comparison, a simple LiC6/S cell using the same sulfur/sulfur compound-containing cathode combined with a prelithated graphite anode shows poor electrochemical performance. - Although higher amounts of graphite can result in a larger initial capacity using the hybrid anodes described herein, capacity fading is also more pronounced with increasing LiC6 content. This can be attributed to the increased thickness and available surface area of graphite incorporated in the hybrid anode. Because an equivalent amount of electrolyte is used in all tests and the graphite faces the separator, the accessibility of electrolyte, and subsequent dissolved polysulfide species, to the Li metal electrode is reduced. Therefore sulfur, and polysulfide, reactions are primarily confined to the graphite preferentially over the Li metal surfaces. For this reason, the total surface area of graphite dictates the amount of “wasted” sulfur, i.e. sulfur consumed in surface reactions and SEI formation, on the anode. This can explain why the cycling behavior of cells with higher carbon-to-sulfur ratios is inferior to those with lower amounts of graphite (
FIG. 5 ). To further confirm that a lower surface area of carbon can benefit the hybrid design, a hard carbon (BET surface area: 75.8 m2 g−1) was used to replace graphite (BET surface area: 6.4 m2 g−1) in the hybrid structure. As expected, the performance from cells using the hard carbon/Li anode is worse than those using the original graphite (LiC6)/Li hybrid design. Nevertheless, when compared to traditional Li—S batteries that use Li-metal anodes (FIG. 1 ), there is still a large improvement in performance with the cells containing a hard carbon/Li hybrid anode, further validating the unique benefits of this anode design. In preferred embodiments, the carbon materials have an electrochemical reduction potential very close to Li/Li+ (to facilitate Li+ extraction) combined with a low surface area to reduce undesired side reactions with sulfur species. - In some embodiments, during charging, Li+ ions diffuse back to the metal electrode where they are redeposited. One issue is to determine if the Li ions will preferentially deposit on the Li-foil or the lithiated graphite portions of the hybrid anode. SEM micrographs in
FIG. 6 show the “as prepared” graphite surface of the hybrid anode (FIG. 6A ) and the same surface after 1000 charge/discharge cycles at a 1C rate (FIG. 6B ) in a Li—S cell. Little morphological change has occurred after extensive cycling yet the surface is rich in sulfur as determined by elemental mapping. After long-term cycling, the morphology of the corresponding Li-foil surface (facing the graphite) is shown inFIGS. 6C and D. There is no evidence of dendritic lithium growth or extensive surface reactions which is dramatically different than the Li metal anodes tested in conventional Li—S cells (FIGS. 2A and 2B ). In addition, minimal amounts of sulfur were observed on the Li metal surface using EDS mapping. These findings suggest that the highly reactive electrolyte/solid domains that cause active mass loss are largely transferred from the Li metal to lithiated graphite. Graphite is an intercalation compound that can accommodate up to 10% volume expansion without mechanical degradation and exposure of new reactive surfaces thus reducing parasitic losses in the cell. Therefore, in some embodiments, cathodes comprising an intercalation compound can be preferred. - The hybrid anodes described herein can be also utilized in lithium-ion batteries having cathodes comprising lithium intercalation compounds. In one instance, a series of test cells using commercially-available materials were prepared. The cathodes in all cells were prepared using a pyrolytic carbon-coated, nanosized, LiFePO4 powder (LFP). The LFP cathodes were then paired with one of three test anodes; (1) Li foil, (2) graphite, or (3) Li foil+graphite configured as a hybrid anode according to embodiments described herein.
- The cathodes were prepared by coating well-dispersed slurries containing 80 wt % LFP powder, 10 wt % Super-P® conductive carbon black, and 10 wt % polyvinylidene difluoride (PVDF) binder dissolved in N-methyl-2-pyrrolidinone (NMP) onto a thin aluminum-foil current collector. The LFP cathode was dried at 70° C. under vacuum for 12 h. A hydraulic press was used to compact the LFP-Al electrode to minimize electrode contact resistance.
- To prepare the hybrid Li-carbon anodes, carbon was pasted or coated onto a thin porous metallic mesh (current collector) and then electrically connected to a Li metal foil with a commercial separator sandwiched between the graphite and Li foil. The carbon material was high power CPreme® graphite material G5 from ConocoPhillips coating/graphitization technology. The separator was not necessary and the hybrid anode could be constructed by simply laminating Li foil to the graphite. Good bonding between the metallic mesh, graphite and conductive carbon minimizes de-lamination, pinholes, and diminished internal cell resistance.
- The porous metal-carbon mesh electrode was prepared by coating well-dispersed slurries containing 80 wt % CPreme® G5 graphite powder, 10 wt % Super-P® conducting carbon black, and 10 wt % PVDF dissolved in NMP onto thin porous copper mesh. The carbon electrodes were dried at 70° C. under vacuum for 12 h, and then hot pressed to form the final carbon laminated electrode. Alternatively, the porous carbon-metallic mesh electrode can be prepared by hot pressing of free-standing carbon thin films onto the thin cooper mesh. The carbon-PTFE composite powder was first obtained by drying well-dispersed slurries containing 80 wt % CPreme® G5 graphite powder, 10 wt % Super-P Li conducting carbon black, and 10 wt % PTFE emulsion diluted in distilled water. The powder was then rolled to form carbon-PTFE free-standing thin films with the desired thickness by a Cavallin flat roller. Finally, the film was hot pressed onto the thin metallic mesh using a Carver hot press.
- All of the coin cells were assembled in an argon-filled glove box with moisture and oxygen contents of less than 1 ppm. Lithium metal disks (Φ15 size and 0.5 mm thickness) were used as the anode for traditional Li-LFP cells and as the metal electrode of the hybrid anode for hybrid cells. The battery-grade electrolyte (Purolyte®) contained 1M LiPF6 dissolved in a mixture of ethyl carbonate/dimethyl carbonate/diethyl carbonate EC/DMC/DEC=1:1:1 (volume ratio). A microporous membrane (Celgard 3501®, 25 μm thickness) was used as the separator. To assemble the hybrid cells, the LFP cathode, a first separator, carbon-metallic mesh electrode, thin metallic ring, a second separator, and lithium foil were punched into Φ15, Φ19, Φ15, Φ15, Φ13 and Φ15 sizes, respectively, and electrolyte was added into each cell layer-by-layer, using a pipette. In one design, the metallic mesh was calendared and punched into metallic rings ˜25 μm in thickness to form the electrical contact between the two components of the hybrid anode. Alternatively, the metallic ring can be replaced by small pieces of metallic mesh to make edge point contact between the lithium foil and carbon-metallic mesh electrode. The layers of the hybrid anode can be separated by the second separator, or sandwiched together directly. All cell components were then carefully aligned, integrated and sealed using a compact hydraulic crimping machine to form the final test device.
- Electrochemical tests were performed using 2325 coin cells in an ambient environment. The galvanostatic discharge-charge test was conducted using a BT-2043 Arbin® Battery Testing System. The hybrid cells and half cells were cycled at different current rates in the voltage interval of 2.5-4.2V. Due to the initial irreversible loss observed for the control cells, the G5-LFP control cells with graphite anodes were tested between 2-4.2V. All capacity values were calculated on the basis of LFP mass. After cycling, several of the coin cells were disassembled in the charged or discharged state for further analysis.
-
FIG. 7 shows the long-term cycling performance of the three tests cells at high charge/discharge rate (i.e., 38C). The hybrid anode described herein results in greatly improved capacity retention, showing little fade after 3500 cycles. The specific capacity of cells containing graphite, or Li-foil, anodes faded to near zero within 500 cycles. This shows that the hybrid anode design is useful in extending the performance and cycle life of cells/batteries using Li-ion chemistries. - While a number of embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims, therefore, are intended to cover all such changes and modifications as they fall within the true spirit and scope of the invention.
Claims (32)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/532,206 US10673069B2 (en) | 2012-06-25 | 2012-06-25 | Hybrid anodes for energy storage devices |
IN11222DEN2014 IN2014DN11222A (en) | 2012-06-25 | 2013-01-08 | |
EP13808518.8A EP2865032A4 (en) | 2012-06-25 | 2013-01-08 | Hybrid anodes for energy storage devices |
KR1020157001921A KR20150027246A (en) | 2012-06-25 | 2013-01-08 | Hybrid Anodes for Energy Storage Devices |
AU2013281193A AU2013281193A1 (en) | 2012-06-25 | 2013-01-08 | Hybrid anodes for energy storage devices |
CN201380033813.4A CN104521034B (en) | 2012-06-25 | 2013-01-08 | Hydridization negative pole for energy storage device |
CA2876568A CA2876568A1 (en) | 2012-06-25 | 2013-01-08 | Hybrid anodes for energy storage devices |
BR112014032572A BR112014032572A2 (en) | 2012-06-25 | 2013-01-08 | energy storage devices and device operation method |
PCT/US2013/020620 WO2014003825A1 (en) | 2012-06-25 | 2013-01-08 | Hybrid anodes for energy storage devices |
US14/166,389 US9214695B2 (en) | 2012-04-04 | 2014-01-28 | Hybrid anodes for redox flow batteries |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/532,206 US10673069B2 (en) | 2012-06-25 | 2012-06-25 | Hybrid anodes for energy storage devices |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/912,516 Continuation-In-Part US20130273459A1 (en) | 2012-04-04 | 2013-06-07 | Ionic Conductive Chromophores and Nonaqueous Redox Flow Batteries |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/166,389 Continuation-In-Part US9214695B2 (en) | 2012-04-04 | 2014-01-28 | Hybrid anodes for redox flow batteries |
Publications (2)
Publication Number | Publication Date |
---|---|
US20130344354A1 true US20130344354A1 (en) | 2013-12-26 |
US10673069B2 US10673069B2 (en) | 2020-06-02 |
Family
ID=49774701
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/532,206 Active 2035-05-06 US10673069B2 (en) | 2012-04-04 | 2012-06-25 | Hybrid anodes for energy storage devices |
Country Status (9)
Country | Link |
---|---|
US (1) | US10673069B2 (en) |
EP (1) | EP2865032A4 (en) |
KR (1) | KR20150027246A (en) |
CN (1) | CN104521034B (en) |
AU (1) | AU2013281193A1 (en) |
BR (1) | BR112014032572A2 (en) |
CA (1) | CA2876568A1 (en) |
IN (1) | IN2014DN11222A (en) |
WO (1) | WO2014003825A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220247039A1 (en) * | 2019-05-24 | 2022-08-04 | University Of Southern California | Long-life lithium-sulfur battery using a novel flexible bi-layer solid state electrolyte |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4419424A (en) * | 1981-07-14 | 1983-12-06 | Julian John D | Electrodes for electrochemical cells current generating cells and rechargeable accumulators |
US5744258A (en) * | 1996-12-23 | 1998-04-28 | Motorola,Inc. | High power, high energy, hybrid electrode and electrical energy storage device made therefrom |
US20090075161A1 (en) * | 2007-09-18 | 2009-03-19 | Fuji Jukogyo Kabushiki Kaisha | Electric storage device |
US20130171502A1 (en) * | 2011-12-29 | 2013-07-04 | Guorong Chen | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0789483B2 (en) | 1984-05-07 | 1995-09-27 | 三洋化成工業株式会社 | Secondary battery |
JP2709303B2 (en) | 1990-02-20 | 1998-02-04 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery |
JP3065797B2 (en) | 1992-07-29 | 2000-07-17 | 新神戸電機株式会社 | Lithium secondary battery |
JPH10112307A (en) | 1996-10-07 | 1998-04-28 | Haibaru:Kk | Nonaqueous electrolyte secondary battery |
JP2002075446A (en) * | 2000-08-02 | 2002-03-15 | Samsung Sdi Co Ltd | Lithium-sulfur cell |
KR200265012Y1 (en) | 2001-11-19 | 2002-02-20 | 주식회사 뉴턴에너지 | Lithium sulfur battery |
JP2011086554A (en) | 2009-10-16 | 2011-04-28 | Sumitomo Electric Ind Ltd | Nonaqueous electrolyte battery |
KR101209687B1 (en) | 2010-12-03 | 2012-12-10 | 기아자동차주식회사 | Lithium ion-sulfur battery |
CN102368561B (en) * | 2011-10-20 | 2013-10-16 | 中国科学院化学研究所 | Chargeable and dischargeable lithium sulfur cell |
-
2012
- 2012-06-25 US US13/532,206 patent/US10673069B2/en active Active
-
2013
- 2013-01-08 KR KR1020157001921A patent/KR20150027246A/en not_active Application Discontinuation
- 2013-01-08 WO PCT/US2013/020620 patent/WO2014003825A1/en active Application Filing
- 2013-01-08 EP EP13808518.8A patent/EP2865032A4/en not_active Withdrawn
- 2013-01-08 CA CA2876568A patent/CA2876568A1/en not_active Abandoned
- 2013-01-08 IN IN11222DEN2014 patent/IN2014DN11222A/en unknown
- 2013-01-08 CN CN201380033813.4A patent/CN104521034B/en not_active Expired - Fee Related
- 2013-01-08 BR BR112014032572A patent/BR112014032572A2/en not_active IP Right Cessation
- 2013-01-08 AU AU2013281193A patent/AU2013281193A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4419424A (en) * | 1981-07-14 | 1983-12-06 | Julian John D | Electrodes for electrochemical cells current generating cells and rechargeable accumulators |
US5744258A (en) * | 1996-12-23 | 1998-04-28 | Motorola,Inc. | High power, high energy, hybrid electrode and electrical energy storage device made therefrom |
US20090075161A1 (en) * | 2007-09-18 | 2009-03-19 | Fuji Jukogyo Kabushiki Kaisha | Electric storage device |
US20130171502A1 (en) * | 2011-12-29 | 2013-07-04 | Guorong Chen | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same |
Non-Patent Citations (1)
Title |
---|
Cation mixing (Li0.5Fe0.5)2SO4F cathode material for lithium-ion batteries, Sun Yang (孙 洋) et al 2011 Chinese Phys. B 20 126101 * |
Also Published As
Publication number | Publication date |
---|---|
EP2865032A4 (en) | 2016-08-03 |
CA2876568A1 (en) | 2014-01-03 |
CN104521034A (en) | 2015-04-15 |
US10673069B2 (en) | 2020-06-02 |
WO2014003825A1 (en) | 2014-01-03 |
CN104521034B (en) | 2018-02-02 |
EP2865032A1 (en) | 2015-04-29 |
KR20150027246A (en) | 2015-03-11 |
IN2014DN11222A (en) | 2015-10-02 |
BR112014032572A2 (en) | 2017-06-27 |
AU2013281193A1 (en) | 2015-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10497927B2 (en) | Methods of applying self-forming artificial solid electrolyte interface (SEI) layer to stabilize cycle stability of electrodes in lithium batteries | |
Komaba et al. | Influence of manganese (II), cobalt (II), and nickel (II) additives in electrolyte on performance of graphite anode for lithium-ion batteries | |
US10608249B2 (en) | Conformal coating of lithium anode via vapor deposition for rechargeable lithium ion batteries | |
US10326136B2 (en) | Porous carbonized composite material for high-performing silicon anodes | |
US9478794B2 (en) | Electroactive materials for rechargeable batteries | |
US20150364755A1 (en) | Silicon Oxide (SiO) Anode Enabled by a Conductive Polymer Binder and Performance Enhancement by Stabilized Lithium Metal Power (SLMP) | |
US20170309914A1 (en) | Pre-lithiated lithium ion battery cell | |
US20150000118A1 (en) | Method for manufacturing graphene-incorporated rechargeable li-ion battery | |
US20190058211A1 (en) | Ether-based electrolyte system improving or supporting anodic stability of electrochemical cells having lithium-containing anodes | |
US10707530B2 (en) | Carbonate-based electrolyte system improving or supporting efficiency of electrochemical cells having lithium-containing anodes | |
KR101735857B1 (en) | high voltage lithium rechargeable battery | |
US9343736B2 (en) | Lithium compensation for full cell operation | |
CN107004827A (en) | Combination electrode and Li-ion batteries piles and the preparation method of combination electrode including combination electrode | |
US11295901B2 (en) | Hybrid electrode materials for bipolar capacitor-assisted solid-state batteries | |
CN102668190A (en) | Solid electrolyte cell and cathode active material | |
US20210013555A1 (en) | Lithium replenishing rechargeable batteries | |
US20130045417A1 (en) | Non-aqueous electrolyte lithium ion secondary battery | |
CN107437609B (en) | Rechargeable electrochemical lithium ion battery cell | |
EP3316366A1 (en) | Positive electrode of lithium-air battery having side reaction prevention film to which metal catalyst is partially introduced, lithium-air battery having same, and manufacturing method therefor | |
JP2012113842A (en) | Nonaqueous electrolyte battery and manufacturing method thereof | |
KR20150065078A (en) | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
US10840539B2 (en) | Lithium batteries, anodes, and methods of anode fabrication | |
US10673069B2 (en) | Hybrid anodes for energy storage devices | |
US20050069776A1 (en) | Method of producing a rechargeable electrochemical element , and an element made therefrom | |
US20220367850A1 (en) | Cathode with Layers of Anode Reductant and Solid-Electrolyte Interphase |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BATTELLE MEMORIAL INSTITUTE, WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LIU, JUN;HUANG, CHENG;XIAO, JIE;SIGNING DATES FROM 20120613 TO 20120614;REEL/FRAME:028442/0385 |
|
AS | Assignment |
Owner name: U.S. DEPARTMENT OF ENERGY, DISTRICT OF COLUMBIA Free format text: CONFIRMATORY LICENSE;ASSIGNOR:BATTELLE MEMORIAL INSTITUTE, PACIFIC NORTHWEST DIVISION;REEL/FRAME:028828/0898 Effective date: 20120710 |
|
AS | Assignment |
Owner name: BATTELLE MEMORIAL INSTITUTE, WASHINGTON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WANG, WEI;XIAO, JIE;WEI, XIAOLIANG;AND OTHERS;SIGNING DATES FROM 20140114 TO 20140128;REEL/FRAME:032066/0548 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2551); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 4 |